Production process of antioxidant 330

Abstract

The invention relates to the technical field of antioxidant production, in particular to a production process of an antioxidant 330, which comprises the following steps: adding dichloromethane, mesitylene and a solid acid catalyst into a reaction kettle, mixing and stirring uniformly, and then dropwise adding a dichloromethane solution of 3, 5-di-tert-butyl-4-hydroxybenzyl methyl ether at room temperature; s2, after dropwise adding is completed, the reaction kettle is heated to continue the reaction, and reaction completion liquid is obtained after the reaction is completed; and S3, filtering and separating the solid acid catalyst and a crude product organic phase from the reaction completion liquid, and refining the crude product organic phase to obtain the antioxidant 330. According to the invention, the service life of equipment is prolonged, the reaction efficiency and the yield and purity of the antioxidant 330 are improved, the solid acid catalyst is easy to separate and recover, the environmental pollution is small, and the service life is long.

Description

Technical Field

[0001] The present invention relates to the technical field of antioxidant production, and particularly to a production process of antioxidant 330. Background Art

[0002] Antioxidant 330 is an antioxidant widely used in the fields of rubber, plastics, lubricating oils, etc., which can effectively prevent the performance degradation of materials caused by oxidation during processing, storage and use. At present, the mainstream industrialization scheme of antioxidant 330 is generally as follows: First, 2,6-di-tert-butylphenol and excessive paraformaldehyde react in the presence of a basic catalyst to generate 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether (i.e., benzyl ether), and then benzyl ether reacts with mesitylene to obtain antioxidant 330. In the prior art, concentrated sulfuric acid is mostly used as a catalyst when benzyl ether and mesitylene react. The concentrated sulfuric acid is dropped into the reaction system to catalyze the reaction. During the reaction process, benzyl ether needs to be greatly in excess, and a large amount of antioxidant 702 will be generated, reducing the economic benefits. In addition, this method also has problems such as long reaction time, low yield and purity of the product, complex post-treatment, and environmental pollution.

[0003] The invention patent with the authorization announcement number CN108503512B discloses a method for synthesizing antioxidant 330 with a novel catalyst, preparing a tetrairon trioxide-molecular sieve supported phosphoric acid catalyst. In the presence of the tetrairon trioxide-molecular sieve supported phosphoric acid catalyst, 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether reacts with mesitylene to obtain antioxidant 330. In this synthesis process, the catalyst is easy to separate and recycle, and the post-treatment is simple. However, the catalytic efficiency of this catalyst and the yield and purity of antioxidant 330 prepared by using this catalyst need to be improved.

[0004] In summary, there is an urgent need to provide a production process of antioxidant 330 that has no corrosion to equipment, high catalytic efficiency, easy separation and recycling of the catalyst, small environmental pollution, long service life, and can obtain high yield and high purity. Summary of the Invention

[0005] To solve at least one of the above problems, the present invention provides a production process of antioxidant 330, including the following steps: S1, adding dichloromethane, mesitylene and a solid acid catalyst into a reaction kettle, mixing and stirring evenly, and then dropping a dichloromethane solution of 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether at room temperature; the solid acid catalyst includes sulfamic acid / ZSM-5 molecular sieve and sulfated zirconia / ZSM-5 molecular sieve with a mass ratio of 1:(1-2); the sulfamic acid content in the sulfamic acid / ZSM-5 molecular sieve is 20-40wt%, and the sulfated zirconia content in the sulfated zirconia / ZSM-5 molecular sieve is 15-35wt%; S2. After the dropping is completed, the temperature of the reaction kettle is raised to continue the reaction. After the reaction is completed, a reaction completion solution is obtained; S3. The solid acid catalyst and the crude organic phase are separated by filtration from the reaction completion solution. After the crude organic phase is refined, antioxidant 330 is obtained.

[0006] In the above technical solution, the solid acid catalyst is used in the reaction system to replace the traditional concentrated sulfuric acid catalyst, avoiding the corrosion of the equipment by concentrated sulfuric acid and the pollution to the environment, greatly improving the service life of the equipment, being green and environmentally friendly. The solid acid catalyst is composed of sulfamic acid / ZSM-5 molecular sieve and sulfated zirconia / ZSM-5 molecular sieve. The synergistic effect of sulfamic acid, sulfated zirconia and ZSM-5 molecular sieve can greatly improve the reaction efficiency, increase the yield and purity of antioxidant 330. The solid acid catalyst has a long service life, is easy to separate and recycle, and has simple post-treatment, improving the production efficiency; in the present invention, the feeding method of dropping the dichloromethane solution of 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether is adopted, and the molar ratio of mesitylene to 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether in the reaction can be reduced to 1:(3.1-3.5). In the prior art, when the reaction is carried out by the feeding method of dropping concentrated sulfuric acid, the molar ratio of mesitylene to 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether in the reaction is 1:3.9. The present invention not only greatly reduces the dosage of 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether, increases the yield of antioxidant 330, but also reduces the purity requirement for 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether. Using 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether with a purity of 92-98% can achieve good reaction effects, increasing the atom utilization rate.

[0007] Preferably, in step S1, the dropping time is 1-2 h; in step S2, the reaction temperature is 40-45 °C and the reaction time is 1-3 h; in step S3, the refining includes: adding n-heptane to the crude organic phase, distilling to displace dichloromethane to obtain a displaced organic phase, cooling the displaced organic phase for crystallization, filtering the precipitated crystals and rinsing them with methanol, and finally drying to obtain antioxidant 330; the distillation temperature is 60-80 °C, and the mass of the added n-heptane is 1.5-3 times the mass of the crude organic phase; the crystallization temperature is 10-15 °C and the crystallization time is 1-1.5 h.

[0008] In the above technical solution, since a solid acid catalyst is used to replace concentrated sulfuric acid, it is not necessary to neutralize the crude organic phase to remove the residual concentrated sulfuric acid, and the post-treatment efficiency is greatly improved. At the same time, environmental pollution is also avoided. In the prior art, when refining the crude organic phase, dichloromethane is first removed by distillation to obtain the concentrated crude organic phase, and then n-heptane is added to the concentrated crude organic phase. After heating under reflux for a certain time, it is cooled to room temperature for crystallization. The process steps are numerous and the production efficiency is low. In the present invention, n-heptane is first added to the crude organic phase, and then dichloromethane is displaced by distillation to obtain the displaced organic phase. Then the displaced organic phase is cooled for crystallization. The process steps are few and the production efficiency is high. The precipitated crystals are rinsed with methanol, which can remove the trace impurities remaining in the crystals and further improve the purity of antioxidant 330.

[0009] Preferably, in step S1, the mass ratio of dichloromethane, solid acid catalyst, mesitylene, and 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether is (450-550):(5-10):12:(78-88); the concentration of the dichloromethane solution of 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether is (15-20) wt%.

[0010] Preferably, in step S1, the ZSM-5 molecular sieve in the sulfamic acid / ZSM-5 molecular sieve and the sulfated zirconia / ZSM-5 molecular sieve is pretreated. The pretreatment includes: mixing the ZSM-5 molecular sieve evenly with an aqueous urea solution with a concentration of (5-10) wt%, heating to 80-100 °C under stirring for reflux reaction for 5-10 h, filtering, washing with water, drying at 110 °C, and calcining at 550 °C for 6 h to obtain the pretreated ZSM-5 molecular sieve; the mass ratio of the ZSM molecular sieve to the aqueous urea solution is 1:(100-200).

[0011] In the above technical solution, using the ammonia gas in-situ generated by the hydrolysis of the aqueous urea solution as the base source to perform desilication treatment on the ZSM-5 molecular sieve can obtain a ZSM-5 molecular sieve with hierarchical pores, improving the loading amount and catalytic performance of ZSM-5.

[0012] Preferably, in step S1, the preparation of the sulfamic acid / ZSM-5 molecular sieve includes the following steps: Mix urea, ethanol, and ZSM-5 molecular sieve evenly according to a mass ratio of 2:(20-50):(5-10), stir at 55-65 °C for 1-2 h, then remove ethanol by reduced pressure distillation under stirring, dry at 100-110 °C for 1-2 h to obtain urea / ZSM-5 molecular sieve; according to a molar ratio of urea to sulfuric acid of 1:(1.2-1.5), add the urea / ZSM-5 molecular sieve to 65% fuming sulfuric acid, mix and stir evenly, react at 40-45 °C for 12-15 h, cool to room temperature for crystallization after the reaction, filter the crystals, and dry at 100-120 °C for 4-5 h to obtain the sulfamic acid / ZSM-5 molecular sieve.

[0013] In the above technical solution, urea dissolves in ethanol to form an ethanol solution of urea. Heating and stirring can not only increase the solubility of urea in ethanol but also increase the penetration rate of urea into the internal pores of the ZSM-5 molecular sieve, thereby obtaining a uniformly dispersed urea / ZSM-5 molecular sieve. Finally, sulfonation reaction of the urea / ZSM-5 molecular sieve with 65% fuming sulfuric acid can obtain a uniformly dispersed sulfamic acid / ZSM-5 molecular sieve.

[0014] Preferably, in step S1, the preparation of the sulfated zirconia / ZSM-5 molecular sieve includes the following steps: Mix zirconium oxychloride, ethanol, and ZSM-5 molecular sieve evenly according to a mass ratio of 2:(20-50):(5-10), stir at 55-65 °C for 1-2 h, then remove ethanol by reduced pressure distillation under stirring, dry at 100-110 °C for 1-2 h, and then calcine at 350-550 °C for 4-6 h to obtain zirconia / ZSM-5 molecular sieve. Impregnate the zirconia / ZSM-5 molecular sieve in a sulfuric acid solution of 0.4-0.6 mol / L according to a mass ratio of 1:(100-200), stir for 25-35 min and then filter, dry at 150-200 °C for 3-4 h to obtain the sulfated zirconia / ZSM-5 molecular sieve.

[0015] In the above technical solution, zirconium oxychloride dissolves in ethanol to form an ethanol solution of zirconium oxychloride. Heating and stirring can not only increase the solubility of zirconium oxychloride in ethanol but also increase the penetration rate of zirconium oxychloride into the internal pores of the ZSM-5 molecular sieve, thereby obtaining a uniformly dispersed zirconium oxychloride / ZSM-5 molecular sieve. After calcining the zirconium oxychloride / ZSM-5 molecular sieve, a uniformly dispersed zirconia / ZSM-5 molecular sieve is obtained. Finally, reacting the zirconia / ZSM-5 molecular sieve with sulfuric acid can obtain a uniformly dispersed sulfated zirconia / ZSM-5 molecular sieve.

[0016] Preferably, in step S1, the solid acid catalyst is in a hollow strip shape, with an inner layer of sulfamic acid / ZSM-5 zeolite and an outer layer of sulfated zirconia / ZSM-5 zeolite. The length of the catalyst is 10 - 30 mm, the thickness of the inner layer is 1 - 3 mm, and the thickness of the outer layer is 1 - 3 mm.

[0017] In the above technical solution, preparing the solid acid catalyst into a hollow strip shape is beneficial for the filtration and separation of the solid acid catalyst. The sulfated zirconia / ZSM-5 zeolite on the outer layer of the solid acid catalyst can improve the compressive strength and wear resistance of the solid acid catalyst. The inner layer of sulfamic acid / ZSM-5 zeolite is in a hollow structure, which can increase the contact area between the sulfamic acid / ZSM-5 zeolite and the reaction materials and improve the catalytic efficiency.

[0018] Preferably, the inner side wall of the inner layer is corrugated, and the outer side wall of the outer layer is corrugated. In the above technical solution, both the inner and outer side walls of the solid acid catalyst are corrugated, which can increase the specific surface area of the sulfated zirconia / ZSM-5 zeolite and the sulfamic acid / ZSM-5 zeolite and further improve the catalytic effect.

[0019] Preferably, the preparation of the hollow strip-shaped solid acid catalyst includes the following steps: S11, mixing sulfamic acid / ZSM-5 zeolite and aluminum sol and stirring evenly to obtain an inner layer extrusion material; S12, mixing sulfated zirconia / ZSM-5 zeolite and aluminum sol and stirring evenly to obtain an outer layer extrusion material; S13, putting the inner layer extrusion material and the outer layer extrusion material into an extruder, extruding and drying to obtain a hollow strip-shaped solid acid catalyst.

[0020] In the above technical solution, by adjusting the shape of the extrusion head of the extruder, a hollow strip-shaped solid acid catalyst with smooth inner and outer side walls and a hollow strip-shaped solid acid catalyst with corrugated inner and outer side walls can be obtained.

[0021] Preferably, in step S11, the mass ratio of sulfamic acid / ZSM-5 zeolite to aluminum sol is 100:(40 - 50), and the solid content of the aluminum sol is 20 wt%; in step S12, the mass ratio of sulfated zirconia / ZSM-5 zeolite to aluminum sol is 100:(40 - 50), and the solid content of the aluminum sol is 20 wt%; in step S13, the drying temperature is 120 - 160 °C, and the drying time is 2 - 3 h.

[0022] Compared with the prior art, the present invention has the following beneficial technical effects: 1. The present invention uses a solid acid catalyst for catalysis, avoiding the corrosion of equipment and environmental pollution and improving the post-treatment efficiency; 2. The solid acid catalyst consists of sulfamic acid / ZSM-5 molecular sieve and sulfated zirconia / ZSM-5 molecular sieve. The synergistic effect of sulfamic acid, sulfated zirconia and ZSM-5 molecular sieve can significantly improve the reaction efficiency, and increase the yield and purity of antioxidant 330. In addition, the solid acid catalyst has a long service life, is easy to separate and recycle, has simple post-treatment, and is green and environmentally friendly. 3. The present invention adopts the feeding method of dropping the dichloromethane solution of 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether, which not only greatly reduces the dosage of 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether, improves the yield of antioxidant 330, but also reduces the purity requirement for 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether. Using 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether with a purity of 92-98% can achieve good reaction effects, and increases the atom utilization rate. 4. The solid acid catalyst is prepared into a hollow strip shape, with the inner layer being sulfamic acid / ZSM-5 molecular sieve and the outer layer being sulfated zirconia / ZSM-5 molecular sieve. The hollow strip-shaped solid acid catalyst is easier to filter and separate. The sulfated zirconia / ZSM-5 molecular sieve on the outer layer of the solid acid catalyst can improve the compressive strength and wear resistance of the solid acid catalyst. The inner layer of sulfamic acid / ZSM-5 molecular sieve is a hollow structure, which can increase the contact area between the sulfamic acid / ZSM-5 molecular sieve and the reaction materials and improve the catalytic efficiency. 5. The inner and outer side walls of the hollow strip-shaped solid acid catalyst are both corrugated, which can increase the specific surface area of the sulfated zirconia / ZSM-5 molecular sieve and the sulfamic acid / ZSM-5 molecular sieve, and further improve the catalytic effect. In summary, the present invention uses a solid acid catalyst for catalysis, avoiding equipment corrosion and extending the service life of the equipment. By adopting the method of dropping the dichloromethane solution of 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether for feeding, the dosage of 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether is reduced, and the reaction efficiency, as well as the yield and purity of antioxidant 330, are improved. The solid acid catalyst is easy to separate and recycle, has little environmental pollution, and has a long service life. Detailed Embodiments

[0023] In order to more clearly understand the above objects, features and advantages of the present invention, the present invention will be further described in detail below in conjunction with specific embodiments. It should be noted that, without conflict, the embodiments of the present application and the features in the embodiments can be combined with each other.

[0024] Many specific details are set forth in the following description in order to fully understand the present invention. However, the present invention can also be implemented in other ways different from those described herein. Therefore, the protection scope of the present invention is not limited by the specific embodiments disclosed below.

[0025] Example 1-1 In this example, a solid acid catalyst A was prepared, including the following steps: Urea, ethanol and ZSM-5 molecular sieve were mixed evenly according to a mass ratio of 2:20:5, stirred at 60°C for 1.5 h, and then ethanol was removed by reduced pressure distillation under stirring conditions. After drying at 100°C for 1 h, urea / ZSM-5 molecular sieve was obtained; according to a molar ratio of urea to sulfuric acid of 1:1.5, the urea / ZSM-5 molecular sieve was added to 65% fuming sulfuric acid in three portions, mixed and stirred evenly, reacted at 40°C for 15 h, cooled to room temperature for crystallization after the reaction, and the crystals were filtered and dried at 100°C for 5 h to obtain sulfamic acid / ZSM-5 molecular sieve, and the content of sulfamic acid was 31 wt%.

[0026] Zirconium oxychloride, ethanol and ZSM-5 molecular sieve were mixed evenly according to a mass ratio of 2:20:5, stirred at 60°C for 1.5 h, and then ethanol was removed by reduced pressure distillation under stirring conditions. After drying at 100°C for 1 h, it was calcined at 450°C for 5 h to obtain zirconia / ZSM-5 molecular sieve. According to a mass ratio of 1:100, the zirconia / ZSM-5 molecular sieve was impregnated in a 0.6 mol / L sulfuric acid solution, stirred for 35 min and then filtered, and dried at 200°C for 3 h to obtain sulfated zirconia / ZSM-5 molecular sieve, and the content of sulfated zirconia was 25 wt%.

[0027] The sulfamic acid / ZSM-5 molecular sieve and the sulfated zirconia / ZSM-5 molecular sieve were mixed evenly according to a mass ratio of 1:2 to obtain the solid acid catalyst A.

[0028] Example 1-2 In this example, a solid acid catalyst B was prepared, including the following steps: ZSM-5 molecular sieve and a 5 wt% aqueous urea solution were mixed evenly according to a mass ratio of 1:100, heated to 90°C for reflux reaction for 6 h under stirring, filtered, washed with water, dried at 110°C for 2 h, and calcined at 550°C for 6 h to obtain pretreated ZSM-5 molecular sieve.

[0029] Urea, ethanol and pretreated ZSM-5 molecular sieve were mixed evenly according to a mass ratio of 2:20:5, stirred at 60°C for 1.5 h, and then ethanol was removed by reduced pressure distillation under stirring conditions. After drying at 100°C for 1 h, urea / ZSM-5 molecular sieve was obtained; according to a molar ratio of urea to sulfuric acid of 1:1.5, the urea / ZSM-5 molecular sieve was added to 65% fuming sulfuric acid in three portions, mixed and stirred evenly, reacted at 40°C for 15 h, cooled to room temperature for crystallization after the reaction, and the crystals were filtered and dried at 100°C for 5 h to obtain sulfamic acid / ZSM-5 molecular sieve, and the content of sulfamic acid was 34 wt%.

[0030] Mix zirconium oxychloride, ethanol, and pretreated ZSM-5 zeolite evenly at a mass ratio of 2:20:5, stir at 60 °C for 1.5 h, then distill off ethanol under reduced pressure with stirring, dry at 100 °C for 1 h, and calcine at 450 °C for 5 h to obtain zirconia / ZSM-5 zeolite. Immerse the zirconia / ZSM-5 zeolite in a 0.6 mol / L sulfuric acid solution at a mass ratio of 1:100, stir for 35 min, then filter, and dry at 200 °C for 3 h to obtain sulfated zirconia / ZSM-5 zeolite, with the content of sulfated zirconia being 28 wt%.

[0031] Mix the sulfamic acid / ZSM-5 zeolite and the sulfated zirconia / ZSM-5 zeolite evenly at a mass ratio of 1:2 to obtain the solid acid catalyst B.

[0032] Examples 1 - 3 In this example, a solid acid catalyst C was prepared, including the following steps: Mix ZSM-5 zeolite and an aqueous urea solution with a concentration of 10 wt% evenly at a mass ratio of 1:200, heat to 90 °C under stirring and reflux for 6 h, filter, wash with water after the reaction, dry at 110 °C for 2 h, and calcine at 550 °C for 6 h to obtain the pretreated ZSM-5 zeolite.

[0033] Mix urea, ethanol, and pretreated ZSM-5 zeolite evenly at a mass ratio of 2:20:5, stir at 60 °C for 1.5 h, then distill off ethanol under reduced pressure with stirring, and dry at 100 °C for 1 h to obtain urea / ZSM-5 zeolite; according to the molar ratio of urea to sulfuric acid of 1:1.5, add the urea / ZSM-5 zeolite to 65% fuming sulfuric acid in three portions, mix and stir evenly, react at 40 °C for 15 h, cool to room temperature for crystallization after the reaction, filter the crystals, and dry at 100 °C for 5 h to obtain the sulfamic acid / ZSM-5 zeolite, with the content of sulfamic acid being 36 wt%.

[0034] Mix zirconium oxychloride, ethanol, and pretreated ZSM-5 zeolite evenly at a mass ratio of 2:20:5, stir at 60 °C for 1.5 h, then distill off ethanol under reduced pressure with stirring, dry at 100 °C for 1 h, and calcine at 450 °C for 5 h to obtain zirconia / ZSM-5 zeolite. Immerse the zirconia / ZSM-5 zeolite in a 0.6 mol / L sulfuric acid solution at a mass ratio of 1:100, stir for 35 min, then filter, and dry at 200 °C for 3 h to obtain sulfated zirconia / ZSM-5 zeolite, with the content of sulfated zirconia being 30 wt%.

[0035] Mix the sulfamic acid / ZSM-5 molecular sieve and the sulfated zirconia / ZSM-5 molecular sieve evenly according to a mass ratio of 1:2 to obtain the solid acid catalyst C.

[0036] Examples 1-4 In this example, the solid acid catalyst D was prepared, including the following steps: Mix the ZSM-5 molecular sieve and the 10 wt% urea aqueous solution evenly according to a mass ratio of 1:200. Under stirring, heat to 90 °C and reflux for 6 h. After the reaction, filter, wash with water, dry at 110 °C for 2 h, and calcine at 550 °C for 6 h to obtain the pretreated ZSM-5 molecular sieve.

[0037] Mix urea, ethanol and the pretreated ZSM-5 molecular sieve evenly according to a mass ratio of 2:20:10. Stir at 60 °C for 1.5 h, then distill off ethanol under reduced pressure under stirring conditions, and dry at 100 °C for 1 h to obtain the urea / ZSM-5 molecular sieve. According to a molar ratio of urea to sulfuric acid of 1:1.5, add the urea / ZSM-5 molecular sieve to 65% fuming sulfuric acid in three portions, mix and stir evenly, react at 40 °C for 15 h, cool to room temperature for crystallization after the reaction, filter the crystals and dry at 100 °C for 5 h to obtain the sulfamic acid / ZSM-5 molecular sieve, and the content of sulfamic acid is 21 wt%.

[0038] Mix zirconium oxychloride, ethanol and the pretreated ZSM-5 molecular sieve evenly according to a mass ratio of 2:20:10. Stir at 60 °C for 1.5 h, then distill off ethanol under reduced pressure under stirring conditions, dry at 100 °C for 1 h and then calcine at 450 °C for 5 h to obtain the zirconia / ZSM-5 molecular sieve. Immerse the zirconia / ZSM-5 molecular sieve in a 0.6 mol / L sulfuric acid solution according to a mass ratio of 1:100, stir for 35 min and then filter, and dry at 200 °C for 3 h to obtain the sulfated zirconia / ZSM-5 molecular sieve, and the content of sulfated zirconia is 18 wt%.

[0039] Mix the sulfamic acid / ZSM-5 molecular sieve and the sulfated zirconia / ZSM-5 molecular sieve evenly according to a mass ratio of 1:2 to obtain the solid acid catalyst D.

[0040] Examples 1-5 In this example, the solid acid catalyst E was prepared. On the basis of Examples 1-3, mix the sulfamic acid / ZSM-5 molecular sieve and the sulfated zirconia / ZSM-5 molecular sieve evenly according to a mass ratio of 1:1 to obtain the solid acid catalyst E.

[0041] Examples 1-6 In this example, the hollow strip-shaped solid acid catalyst F was prepared, including the following steps: Mix the sulfamic acid / ZSM-5 molecular sieve in Examples 1-3 with an aluminum sol having a solid content of 20 wt% evenly at a mass ratio of 100:40 to obtain an inner layer extrusion material; Mix the sulfated zirconia / ZSM-5 molecular sieve in Examples 1-3 with an aluminum sol having a solid content of 20 wt% evenly at a mass ratio of 100:40 to obtain an outer layer extrusion material; Put the inner layer extrusion material and the outer layer extrusion material into an extruder at a mass ratio of 1:2 and extrude, then dry at 120 °C for 3 h to obtain a hollow strip-shaped solid acid catalyst F. The solid acid catalyst F has a length of 10 mm, an inner layer thickness of 2.5 mm, and an outer layer thickness of 3 mm.

[0042] Examples 1-7 In this example, a hollow strip-shaped solid acid catalyst G was prepared. On the basis of Examples 1-6, put the inner layer extrusion material and the outer layer extrusion material into an extruder at a mass ratio of 1:1.5 and extrude, then dry at 120 °C for 3 h to obtain a hollow strip-shaped solid acid catalyst G. The solid acid catalyst G has a length of 10 mm, an inner layer thickness of 3 mm, and an outer layer thickness of 2 mm.

[0043] Examples 1-8 In this example, a hollow strip-shaped solid acid catalyst H was prepared. On the basis of Examples 1-6, put the inner layer extrusion material and the outer layer extrusion material into an extruder at a mass ratio of 1:1 and extrude, then dry at 120 °C for 3 h to obtain a hollow strip-shaped solid acid catalyst H. The solid acid catalyst H has a length of 10 mm, an inner layer thickness of 2 mm, and an outer layer thickness of 1 mm.

[0044] Examples 1-9 In this example, a hollow strip-shaped solid acid catalyst I was prepared. On the basis of Examples 1-6, put the inner layer extrusion material and the outer layer extrusion material into an extruder at a mass ratio of 1:2 and extrude, then dry at 120 °C for 3 h to obtain a hollow strip-shaped solid acid catalyst I. The solid acid catalyst I has a length of 10 mm, the inner side wall of the inner layer is corrugated, the thickness at the trough of the inner layer is 2 mm, the outer side wall of the outer layer is corrugated, and the thickness at the trough of the outer layer is 2 mm.

[0045] Examples 2-1 This example provides a production process of antioxidant 330, including the following steps: Add 120 parts by mass of dichloromethane, 12 parts by mass of mesitylene, and 5 parts by mass of solid acid catalyst A into a reaction kettle, mix and stir evenly, and then dropwise add 415 parts by mass of a dichloromethane solution of 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether with a concentration of 20 wt% at room temperature for 1.5 h; among them, 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether is synthesized by a conventional route in the prior art, and is formed by reacting 2,6-di-tert-butylphenol with excessive paraformaldehyde in the presence of a basic catalyst, and the purity is 92%; After the dropping is completed, heat the reaction kettle to 45 °C and continue the reaction for 1 h to obtain a reaction completion liquid after the reaction is completed; Filter and separate the solid acid catalyst A and the crude organic phase from the reaction completion liquid, and obtain antioxidant 330 after refining the crude organic phase; the refining includes: adding n-heptane with a mass twice that of the crude organic phase to the crude organic phase, distilling and replacing dichloromethane at 60 °C to obtain a replaced organic phase, cooling the replaced organic phase to 10 °C for crystallization for 1 h, filtering the precipitated crystals, rinsing with methanol, and finally drying to obtain antioxidant 330. The yield of antioxidant 330 is 89.1%, and the purity is 99.3%.

[0046] Example 2-2 This example provides a production process of antioxidant 330. On the basis of Example 2-1, replace solid acid catalyst A with solid acid catalyst B, and the rest is the same as Example 2-1. The yield of antioxidant 330 is 89.7%, and the purity is 99.4%.

[0047] Example 2-3 This example provides a production process of antioxidant 330. On the basis of Example 2-1, replace solid acid catalyst A with solid acid catalyst C, and the rest is the same as Example 2-1. The yield of antioxidant 330 is 90.5%, and the purity is 99.6%.

[0048] Example 2-4 This example provides a production process of antioxidant 330. On the basis of Example 2-1, replace solid acid catalyst A with solid acid catalyst D, and the rest is the same as Example 2-1. The yield of antioxidant 330 is 89.1%, and the purity is 99.2%.

[0049] Example 2-5 This example provides a production process of antioxidant 330. On the basis of Example 2-1, replace solid acid catalyst A with solid acid catalyst E, and the rest is the same as Example 2-1. The yield of antioxidant 330 is 89.5%, and the purity is 99.5%.

[0050] Example 2-6 This example provides a production process of antioxidant 330. On the basis of Example 2-1, solid acid catalyst A is replaced with solid acid catalyst F, and the rest is the same as Example 2-1. The yield of antioxidant 330 is 90.7%, and the purity is 99.6%.

[0051] Example 2-7 This example provides a production process of antioxidant 330. On the basis of Example 2-1, solid acid catalyst A is replaced with solid acid catalyst G, and the rest is the same as Example 2-1. The yield of antioxidant 330 is 90.1%, and the purity is 99.4%.

[0052] Example 2-8 This example provides a production process of antioxidant 330. On the basis of Example 2-1, solid acid catalyst A is replaced with solid acid catalyst H, and the rest is the same as Example 2-1. The yield of antioxidant 330 is 89.8%, and the purity is 99.4%.

[0053] Example 2-9 This example provides a production process of antioxidant 330. On the basis of Example 2-1, solid acid catalyst A is replaced with solid acid catalyst I, and the rest is the same as Example 2-1. The yield of antioxidant 330 is 90.9%, and the purity is 99.6%.

[0054] Example 2-10 This example provides a production process of antioxidant 330, including the following steps: Add 150 parts by mass of dichloromethane, 12 parts by mass of mesitylene, and 10 parts by mass of solid acid catalyst I into the reaction kettle and mix and stir evenly. Then, dropwise add 390 parts by mass of a dichloromethane solution of 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether with a concentration of 20 wt% at room temperature for 1 h; among them, 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether is synthesized by a conventional route in the prior art and is formed by the reaction of 2,6-di-tert-butylphenol and excessive paraformaldehyde in the presence of a basic catalyst, and the purity is 96%; After the dropping is completed, heat the reaction kettle to 40 °C and continue the reaction for 3 h. After the reaction is completed, obtain the reaction completion liquid; Filter and separate solid acid catalyst I and the crude organic phase from the reaction completion liquid, and refine the crude organic phase to obtain antioxidant 330; the refining includes: add n-heptane with a mass twice that of the crude organic phase to the crude organic phase, distill and replace dichloromethane at 60 °C to obtain the replaced organic phase, cool the replaced organic phase to 10 °C for crystallization for 1 h, filter the precipitated crystals, wash them with methanol, and finally dry them to obtain antioxidant 330. The yield of antioxidant 330 is 91.2%, and the purity is 99.4%.

[0055] Example 2-11 This example provides a production process of antioxidant 330, which includes the following steps: Add 140 parts by mass of dichloromethane, 12 parts by mass of mesitylene, and 8 parts by mass of solid acid catalyst I into the reaction kettle, mix and stir evenly, and then dropwise add 440 parts by mass of a dichloromethane solution of 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether with a concentration of 20 wt% at room temperature for 1.5 h; among them, 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether is synthesized by a conventional route in the prior art, and is formed by reacting 2,6-di-tert-butylphenol with excessive paraformaldehyde in the presence of a basic catalyst, with a purity of 98%; After the dropping is completed, heat the reaction kettle to 45 °C and continue to react for 1 h to obtain a reaction completion liquid after the reaction is completed; Filter and separate solid acid catalyst I and the crude organic phase from the reaction completion liquid, and obtain antioxidant 330 after refining the crude organic phase; the refining includes: adding n-heptane with a mass twice that of the crude organic phase to the crude organic phase, distilling and replacing dichloromethane at 60 °C to obtain a replaced organic phase, cooling the replaced organic phase to 10 °C for crystallization for 1 h, filtering the precipitated crystals and rinsing them with methanol, and finally drying to obtain antioxidant 330. The yield of antioxidant 330 is 91.6%, and the purity is 99.6%.

[0056] The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above examples. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principle of the present invention shall be equivalent replacement methods and are all included in the protection scope of the present invention.

Claims

1. A production process of antioxidant 330, characterized in that, It includes the following steps: S1. Add dichloromethane, mesitylene and a solid acid catalyst into a reaction kettle, mix and stir evenly, and then dropwise add a dichloromethane solution of 3,5 - di - tert - butyl - 4 - hydroxybenzyl methyl ether at room temperature for 1 - 2 h; the solid acid catalyst includes sulfamic acid / ZSM - 5 molecular sieve and sulfated zirconia / ZSM - 5 molecular sieve with a mass ratio of 1:(1 - 2); the sulfamic acid content in the sulfamic acid / ZSM - 5 molecular sieve is 20 - 40 wt%, and the sulfated zirconia content in the sulfated zirconia / ZSM - 5 molecular sieve is 15 - 35 wt%; S2. After the dropping is completed, heat the reaction kettle to 40 - 45 °C and continue the reaction for 1 - 3 h. After the reaction is completed, a reaction - completed liquid is obtained; S3. Filter and separate the solid acid catalyst and the crude organic phase from the reaction - completed liquid. Add n - heptane with a mass 1.5 - 3 times that of the crude organic phase into the crude organic phase, distill and replace dichloromethane at 60 - 80 °C to obtain a replaced organic phase. Cool the replaced organic phase to 10 - 15 °C for crystallization for 1 - 1.5 h. Filter the precipitated crystals, wash them with methanol, and finally dry them to obtain antioxidant 330.

2. The production process of an antioxidant 330 according to claim 1, characterized in that, In step S1, the mass ratio of dichloromethane, solid acid catalyst, mesitylene and 3,5 - di - tert - butyl - 4 - hydroxybenzyl methyl ether is (450 - 550):(5 - 10):12:(78 - 88); the concentration of the dichloromethane solution of 3,5 - di - tert - butyl - 4 - hydroxybenzyl methyl ether is (15 - 20) wt%.

3. The production process of an antioxidant 330 according to claim 1, characterized in that, In step S1, the ZSM - 5 molecular sieve in the sulfamic acid / ZSM - 5 molecular sieve and the sulfated zirconia / ZSM - 5 molecular sieve is pretreated. The pretreatment includes: mixing the ZSM - 5 molecular sieve evenly with an aqueous urea solution with a concentration of (5 - 10) wt%, heating to 80 - 100 °C under stirring for reflux reaction for 5 - 10 h, filtering, washing with water, drying at 110 °C, and calcining at 550 °C for 6 h to obtain a pretreated ZSM - 5 molecular sieve; the mass ratio of the ZSM molecular sieve to the aqueous urea solution is 1:(100 - 200).

4. The production process of an antioxidant 330 according to claim 1, characterized in that, In step S1, the preparation of the sulfamic acid / ZSM - 5 molecular sieve includes the following steps: Mix urea, ethanol and ZSM - 5 molecular sieve evenly according to a mass ratio of 2:(20 - 50):(5 - 10), stir at 55 - 65 °C for 1 - 2 h, then remove ethanol by reduced - pressure distillation under stirring, and dry at 100 - 110 °C for 1 - 2 h to obtain urea / ZSM - 5 molecular sieve; according to a molar ratio of urea to sulfuric acid of 1:(1.2 - 1.5), add the urea / ZSM - 5 molecular sieve into 65% fuming sulfuric acid, mix and stir evenly, react at 40 - 45 °C for 12 - 15 h, cool to room temperature for crystallization after the reaction is completed, filter the crystals, and dry at 100 - 120 °C for 4 - 5 h to obtain the sulfamic acid / ZSM - 5 molecular sieve.

5. The production process of an antioxidant 330 according to claim 1, characterized in that, In step S1, the preparation of the sulfated zirconia / ZSM - 5 molecular sieve includes the following steps: Mix zirconium oxychloride, ethanol and ZSM-5 molecular sieve evenly according to the mass ratio of 2:(20-50):(5-10), stir at 55-65 °C for 1-2 h, then distill off ethanol under reduced pressure with stirring, dry at 100-110 °C for 1-2 h and then calcine at 350-550 °C for 4-6 h to obtain zirconia / ZSM-5 molecular sieve. Immerse the zirconia / ZSM-5 molecular sieve in 0.4-0.6 mol / L sulfuric acid solution according to the mass ratio of 1:(100-200), stir for 25-35 min and then filter, dry at 150-200 °C for 3-4 h to obtain sulfated zirconia / ZSM-5 molecular sieve.

6. The production process of an antioxidant 330 according to claim 1, characterized in that, In step S1, the solid acid catalyst is in a hollow strip shape, with an inner layer of aminosulfonic acid / ZSM-5 molecular sieve and an outer layer of sulfated zirconia / ZSM-5 molecular sieve. The length of the catalyst is 10-30 mm, the inner layer thickness is 1-3 mm, and the outer layer thickness is 1-3 mm.

7. The production process of an antioxidant 330 according to claim 6, characterized in that, The inner side wall of the inner layer is corrugated, and the outer side wall of the outer layer is corrugated.

8. The production process of an antioxidant 330 according to claim 6, characterized in that, The preparation of the hollow strip-shaped solid acid catalyst includes the following steps: S11, mix aminosulfonic acid / ZSM-5 molecular sieve and aluminum sol evenly and stir to obtain the inner layer extrusion material; S12, mix sulfated zirconia / ZSM-5 molecular sieve and aluminum sol evenly and stir to obtain the outer layer extrusion material; S13, put the inner layer extrusion material and the outer layer extrusion material into an extruder, extrude and dry to obtain the hollow strip-shaped solid acid catalyst.

9. The production process of an antioxidant 330 according to claim 8, characterized in that, In step S11, the mass ratio of aminosulfonic acid / ZSM-5 molecular sieve to aluminum sol is 100:(40-50), and the solid content of the aluminum sol is 20 wt%; in step S12, the mass ratio of sulfated zirconia / ZSM-5 molecular sieve to aluminum sol is 100:(40-50), and the solid content of the aluminum sol is 20 wt%; in step S13, the drying temperature is 120-160 °C and the drying time is 2-3 h.